Aqueous-phase effects on ethanol decomposition over Ru-based catalysts

Zare, Mehdi; Saleheen, Mohammad; Mamun, Osman; Heyden, Andreas

doi:10.1039/d1cy01057c

Title: Aqueous-phase effects on ethanol decomposition over Ru-based catalysts

Journal Article · 06 September 2021 · Catalysis Science and Technology

DOI: https://doi.org/10.1039/d1cy01057c · OSTI ID:1978772

Zare, Mehdi ^[1];

^[1];

^[1]

University of South Carolina, Columbia, SC (United States)

The effects of an aqueous phase on ethanol decomposition for hydrogen production over a Ru(0001) catalyst surface model have been investigated from first principles. Solvent effects on the reaction mechanism and kinetic parameters have been quantified with the help of a microkinetic reactor model, density functional theory, and an implicit solvation scheme (iSMS). Our calculations indicate that in both vapor- and aqueous-phase reaction environments, the ethanol decomposition starts with acetaldehyde formation on the surface, some of which further dehydrogenates to ketenyl species (CHCO), where the C–C bond cleaves to form methylidyne (CH) and CO. In the vapor phase, adsorbed CH gets hydrogenated to methane, and CO desorbs or undergoes methanation reducing the amount of hydrogen produced. In contrast, under aqueous phase reaction conditions, the methanation is inhibited, and the water–gas shift (WGS) reaction is accelerated, leading to complete conversion of CO to CO₂ and H₂. Furthermore, calculations indicate that the observed reaction behavior under aqueous phase reforming conditions originates primarily from the higher water chemical potential, and implicit solvent models predict only a small solvation effect.

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Research Organization:: University of California, Oakland, CA (United States); University of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: Environmental Molecular Sciences Laboratory (EMSL); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); XSEDE

Grant/Contract Number:: AC02-05CH11231; SC0007167

OSTI ID:: 1978772

Journal Information:: Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 20 Vol. 11; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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